Olefin Polymerization catalyst

ABSTRACT

This invention relates to an olefin polymerization catalyst composition comprising the product of the combination of at least one activator and at least two different transition metal compounds each of which is represented by the formula:  
     ((Z)XA t (YJ)) q MQ n   (I)  
     where M is a metal selected from Group 3 to 13 or lanthanide and actinide series of the Periodic Table of Elements; Q is bonded to M and each Q is a monovalent, divalent or trivalent anion; X and Y are bonded to M; X and Y are independently C or a heteroatom, provided that at least one of X and Y is a heteroatom and Y is contained in a heterocyclic ring J, where J comprises from 2 to 50 non-hydrogen atoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms; t is 0 or 1; when t is 1, A is a bridging group joined to at least one of X, Y or J; q is 1 or 2; n is the oxidation state of M minus q if Q is a monovalent anion, n is (the oxidation state of M−q)/2, if Q is a bivalent anion or n is (the oxidation state of M−q)/3 if Q is a trivalent anion.

STATEMENT OF RELATED APPLICATIONS

[0001] This application relates to U.S. Ser. No. 09/103,620 filed Jun.23, 1998 claiming the benefit of provisional application number60/051,581, filed Jul. 2, 1997 and to concurrently filed U.S. patentapplications, Ser. Nos. 09/213,627, 09/216,215, and 09/216,613, allfiled Dec. 18, 1998.

FIELD OF THE INVENTION

[0002] This invention relates to olefin polymerization catalysts basedupon two transition metal compounds comprising bidentate ligandscontaining pyridine or quinoline moieties and mixtures thereof.

BACKGROUND OF THE INVENTION

[0003] The intense commercialization of metallocene polyolefin catalystshas led to widespread interest in the design of non-metallocene,homogeneous catalysts. This field is more than an academic curiosity asnew, non-metallocene catalysts may provide an easier pathway tocurrently available products and may also provide product and processopportunities which are beyond the capability of metallocene catalysts.In addition, certain non-cyclopentadienyl ligands may be more economicaldue to the relative ease of synthesis of a variety of substitutedanalogs.

[0004] Thus there is a need in the art for new novel olefinpolymerization catalysts. WO 96/23101, WO 97/02298, WO 96/33202 andFurhmann et al, Inorg. Chem. 35:6742-6745 (1996) all disclose nitrogencontaining single site like catalyst systems.

SUMMARY OF THE INVENTION

[0005] This invention relates to an olefin polymerization catalystsystem comprising at least one activator and at least two transitionmetal catalysts based on bidentate ligands containing pyridine orquinoline moieties, such as those described in U.S. application Ser. No.09/103,620 filed Jun. 23, 1998, which is herein incorporated byreference.

BRIEF SUMMARY OF THE DRAWINGS

[0006] FIGS. 1-5 are plots of the log of weight average molecular weightversus the dwt/d(logM), a measure of molecular weight distribution forthe runs in Table 1.

[0007]FIGS. 6 and 7 are the size exclusion chromatography (SEC) graphsfor the runs in examples 11 and 12.

DETAILED DESCRIPTION OF THE INVENTION

[0008] This invention relates to olefin polymerization catalyst systemcomprising at least one activator and at least two transition metalcatalysts based on bidentate ligands containing pyridine or quinolinemoieties. The activator may be any known catalyst activator and in oneembodiment is an alkyl aluminum, an alumoxane, a modified alumoxane, apolyalumoxane, a non-coordinating anion, a Lewis acid, a borane or amixture thereof.

[0009] There are a variety of methods for preparing alumoxane andmodified alumoxanes, non-limiting examples of which are described inU.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529,5,693,838, 5,731,253 and 5,731,451 and European publications EP-A-0 561476, EP-B1-0 279 586 and EP-A-0 594-218, and PCT publication WO94/10180, all of which are herein fully incorporated by reference.Methyl alumoxane, modified methylalumoxane, trisobutyl alumoxane, andpolymethylalumoxane are preferred activators.

[0010] Ionizing compounds (non-coordinating anions) may contain anactive proton, or some other cation associated with but not coordinatedto or only loosely coordinated to the remaining ion of the ionizingcompound. Such compounds and the like are described in Europeanpublications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-0 426637, EP-A-500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos.5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,387,568,5,384,299 and 5,502,124 and U.S. patent application Ser. No. 08/285,380,filed Aug. 3, 1994, all of which are herein fully incorporated byreference. Other activators include those described in PCT publicationWO 98/07515 such as tris (2,2′,2″-nonafluorobiphenyl) fluoroaluminate,which is fully incorporated herein by reference. Combinations ofactivators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example, PCTpublications WO 94/07928 and WO 95/14044 and U.S. Pat. Nos. 5,153,157and 5,453,410 all of which are herein fully incorporated by reference.Also, methods of activation such as using radiation and the like arealso contemplated as activators for the purposes of this invention.

[0011] In one embodiment, the transition metal catalyst compound basedon bidentate ligands containing pyridine or quinoline moieties isrepresented by the formula:

((Z)XA_(t)(YJ))_(q)MQ_(n)  (I)

[0012] where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, divalent or trivalent anion; X and Y are bondedto M; X and Y are independently carbon or a heteroatom, provided that atleast one of X and Y is a heteroatom, preferably both X and Y areheteroatoms; Y is contained in a heterocyclic ring J, where J comprisesfrom 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbon atoms; Z isbonded to X, where Z comprises 1 to 50 non-hydrogen atoms, preferably 1to 50 carbon atoms or a silyl group, an alkyl silyl group such as atrialkyl silyl, preferably Z is a cyclic group containing 3 to 50 atoms,preferably 3 to 30 carbon atoms; t is 0 or 1; when t is 1, A is abridging group joined to at least one of X, Y or J, preferably X and J;q is 1 or 2; n is the oxidation state of M minus q minus 1 if Q is amonovalent anion, n is (the oxidation state of M−q)/2, if Q is abivalent anion or n is (the oxidation state of M−q)/3 if Q is atrivalent anion., typically n is an integer from 1 to 4 depending on theoxidation state of M. In one embodiment, if X is oxygen or sulfur then Zis optional. In another embodiment, if X is nitrogen or phosphorous thenZ is present. In an embodiment, Z is preferably an aryl group, morepreferably a substituted aryl group.

[0013] In another embodiment, these the transition metal catalystcompounds are represented by the formula:

((R′_(m)Z)XA(YJR″_(p)))_(q)MQ_(n)  (II)

[0014] where M is a metal selected from Group 3 to 13 of the PeriodicTable of Elements, preferably a Group 4 to 12 transition metal, morepreferably a Group 4, 5 or 6 transition metal, even more preferably aGroup 4 transition metal such as titanium, zirconium or hafnium, andmost preferably zirconium;

[0015] Each Q is bonded to M and each Q is a monovalent, divalent ortrivalent anion. Preferably each Q is independently selected from thegroup consisting of halogens, hydrogen, alkyl, aryl, alkenyl, alkylaryl,arylalkyl, hydrocarboxy or phenoxy radicals having 1-20 carbon atoms.Each Q may also be amides, phosphides, sulfides, silylalkyls,diketonates, and carboxylates. Optionally, each Q may contain one ormore heteroatoms, more preferably each Q is selected from the groupconsisting of halides, alkyl radicals and arylalkyl radicals. Mostpreferably, each Q is selected from the group consisting of arylalkylradicals such as benzyl.

[0016] X and Y are both bound to M and are independently carbon or aheteroatom, provided that at least one of X and Y is a heteroatom, X andY are preferably each heteroatoms, more preferably X and Y areindependently selected from the group consisting of nitrogen, oxygen,sulfur and phosphorous, even more preferably nitrogen or phosphorous,and most preferably nitrogen;

[0017] Y is contained in a heterocyclic ring or ring system J. Jcontains from 2 to 30 carbon atoms, preferably from 2 to 7 carbon atoms,more preferably from 3 to 6 carbon atoms, and most preferably 5 carbonatoms. Optionally, the heterocyclic ring J containing Y, may containadditional heteroatoms. J may be substituted with R″ groups that areindependently selected from the group consisting of hydrogen or linear,branched, cyclic, alkyl radicals, or alkenyl, alkynyl, alkoxy, aryl oraryloxy radicals. Also, two or more R″ groups may be joined to form acyclic moiety such as an aliphatic or aromatic ring. Preferably R″ ishydrogen or an aryl group, most preferably R″ is hydrogen. When R″ is anaryl group and Y is nitrogen, a quinoline group is formed. Optionally,an R″ may be joined to A;

[0018] Z is a hydrocarbyl group bonded to X, preferably Z is ahydrocarbyl group of from 1 to 50 carbon atoms, preferably Z is a cyclicgroup having from 3 to 30 carbon atoms, preferably Z is a substituted orunsubstituted cyclic group containing from 3 to 30 carbon atoms,optionally including one or more heteroatoms, more preferably Z is anaryl group, most preferably a substituted aryl group in anotherembodiment Z may be silyl or an alkyl silyl, preferably a trialkylsilyl;

[0019] Z may be substituted with R′ groups that are independentlyselected from group consisting of hydrogen or linear, branched, alkylradicals or cyclic alkyl, alkenyl, alkynyl or aryl radicals. Also, twoor more R′ groups may be joined to form a cyclic moiety such as analiphatic or aromatic ring. Preferably R′ is an alkyl group having from1 to 20 carbon atoms, more preferably R′ is methyl, ethyl, propyl,butyl, pentyl and the like, including isomers thereof, more preferablyR′ is a methyl group, or a primary, secondary or tertiary hydrocarbon,including isopropyl, t-butyl and the like, most preferably R′ is anisopropyl group. Optionally, an R′ group may be joined to A. It ispreferred that at least one R′ is ortho to X;

[0020] A is a bridging group joined to at least one of, preferably bothof, X and J. Bridging group A contains one or more Group 13 to 16elements from Periodic Table of Elements. More preferably A contains oneor more Group 14 elements, most preferably A is a substituted carbongroup, a di-substituted carbon group or vinyl group; and

[0021] In formula (II) m and p are independently an integer from 0 to 5,preferably m is 2; n is the oxidation state of M minus q minus 1 if Q isa monovalent anion, n is (the oxidation state of M−)/2, if Q is abivalent anion or n is (the oxidation state of M−q)/3 if Q is atrivalent anion, preferably n is an integer from 1 to 4; and q is 1 or2, and where q is 2, the two ((R′_(m)Z)XA(YJR′_(m))) of formula (II) arebridged to each other via a bridging group, preferably a bridging groupcontaining a Group 14 element.

[0022] In a preferred embodiment when n is 2 or 3 in formula I or II andthe second catalyst is the same as the first catalyst except that one Qgroup is a hydrocarboxy group, a boronate or an amide. In a particularlypreferred embodiment when n is 2 or 3 in formula I or II, then thesecond catalyst is the same as the first catalyst except that one Qgroup is an alkoxide, phenoxide, acetylacetonate, carboxylate,cyclopentadienyl, flourenyls or an indenyl group. In anotherparticularly preferred embodiment when n is 2 or 3 in formula I or IIthe second catalyst is the same as the first catalyst except that one Qgroup of the second catalyst is a hydrocarboxy adduct of the analogous Qgroup on the first catalyst, preferably an alkoxide adduct, a boronate,a phenoxide adduct, an acetylacetonate adduct, a carboxylate adduct, anamide adduct, a cyclopentadienyl adduct, a flourenyl adduct or anindenyl adduct.

[0023] In preferred embodiment, at least one of the transition metalcatalyst compounds is represented by the formula:

((Z)XA_(t)(YJ))_(q)MQ_(m)T_(s)  (III)

[0024] where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; T is bonded to M andis an element from Group 13 to 16, preferably oxygen, boron, nitrogen,silicon, phosphorus, sulfur or aluminum and T may also be bound to oneor more C1 to C50 groups optionally containing one or more heteroatoms,preferably T is a hydrocarboxy group, a boronate group or an amidegroup, preferably an alkoxide, phenoxide, acetylacetonate, orcarboxylate or a cyclopentadienide group such as cyclopentadienyls,flourenyls and indenyls, Q is bonded to M and each Q is a monovalent,divalent or trivalent anion; X and Y are bonded to M; X and Y areindependently C or a heteroatom, provided that at least one of X and Yis a heteroatom, preferably both X and Y are heteroatoms; Y is containedin a heterocyclic ring J, where J comprises from 2 to 50 non-hydrogenatoms, preferably 2 to 30 carbon atoms; Z is bonded to X, where Zcomprises 1 to 50 non-hydrogen atoms, preferably 1 to 50 carbon atoms,preferably Z is a cyclic group containing 3 to 50 atoms, preferably 3 to30 carbon atoms, alternately Z may be a silyl group, preferably an alkylsilyl group; t is 0 or 1; when t is 1, A is a bridging group joined toat least one of X, Y or J, preferably X and J; q is 1 or 2; m is theoxidation state of M minus q minus s if Q is a monovalent anion, m is(the oxidation state of M−q−s)/2, if Q is a bivalent anion or m is (theoxidation state of M−q−s)/3 if Q is a trivalent anion, preferably m isan integer from 1 to 3, s is 1, 2 or 3, preferably 1 or 2. In oneembodiment, where X is oxygen or sulfur then Z is optional. In anotherembodiment, where X is nitrogen or phosphorous then Z is present. In apreferred embodiment T is oxygen and is bound to an alkyl, aryl, oralkaryl group.

[0025] In another embodiment, at least one of the transition metalcatalyst compounds is represented by the formula:

((R′_(m)Z)XA(YJR″_(p)))_(q)MQ_(n)T_(s)  (IV)

[0026] where M is a metal selected from Group 3 to 13 of the PeriodicTable of Elements, preferably a Group 4 to 12 transition metal, morepreferably a Group 4, 5 or 6 transition metal, even more preferably aGroup 4 transition metal such as titanium, zirconium or hafnium, andmost preferably zirconium;

[0027] T is bonded to M and is an element from Group 13 to 16,preferably oxygen, boron, nitrogen, silicon, phosphorus, sulfur oraluminum and T may also be bound to one or more C1 to C50 groupsoptionally containing one or more heteroatoms, T is preferably ahydrocarboxy group, a boronate, or an amide, preferably an alkoxide,phenoxide, acetylacetonate, or carboxylate or a cyclopentadienide groupsuch as cyclopentadienyls, flourenyls and indenyls.

[0028] Each Q is bonded to M and each Q is a monovalent, divalent ortrivalent anion. Preferably each Q is independently selected from thegroup consisting of halogens, hydrogen, alkyl, aryl, alkenyl, alkylaryl,arylalkyl, hydrocarboxy or phenoxy radicals having 1-20 carbon atoms.Each Q may also be amides, phosphides, sulfides, silylalkyls,diketonates, and carboxylates. Optionally, each Q may contain one ormore heteroatoms, more preferably each Q is selected from the groupconsisting of halides, alkyl radicals and arylalkyl radicals. Mostpreferably, each Q is selected from the group consisting of arylalkylradicals such as benzyl.

[0029] X and Y are independently C or a heteroatom, provided that atleast one of X and Y is a heteroatom, X and Y are preferably eachheteroatoms, more preferably independently selected from the groupconsisting of nitrogen, oxygen, sulfur and phosphorous, even morepreferably nitrogen or phosphorous, and most preferably nitrogen;

[0030] Y is contained in a heterocyclic ring or ring system J. Scontains from 2 to 30 carbon atoms, preferably from 2 to 7 carbon atoms,more preferably from 3 to 6 carbon atoms, and most preferably 5 carbonatoms. Optionally, the heterocyclic ring J containing Y, may containadditional heteroatoms. J may be substituted with R″ groups that areindependently selected from the group consisting of hydrogen or linear,branched, cyclic, alkyl radicals, or alkenyl, alkynyl, alkoxy, aryl oraryloxy radicals. Also, two or more R″ groups may be joined to form acyclic moiety such as an aliphatic or aromatic ring. Preferably R″ ishydrogen or an aryl group, most preferably R″ is hydrogen. When R″ is anaryl group and Y is nitrogen, a quinoline group is formed. Optionally,an R″ may be joined to A;

[0031] Z is a hydrocarbyl group bonded to X, preferably Z is ahydrocarbyl group of from 1 to 50 carbon atoms, preferably Z is a cyclicgroup having from 3 to 30 carbon atoms, preferably Z is a substituted orunsubstituted cyclic group containing from 3 to 30 carbon atoms,optionally including one or more heteroatoms, Z may be a silyl group, analkylsilyl group or a trialkyl, in another embodiment Z is not an arylgroup;

[0032] Z may be substituted with R′ groups that are independentlyselected from group consisting of hydrogen or linear, branched, alkylradicals or cyclic alkyl, alkenyl, or alkynyl radicals. Also, two ormore R′ groups may be joined to form a cyclic moiety such as analiphatic or aromatic ring. Preferably R′ is an alkyl group having from1 to 20 carbon atoms, more preferably R′ is methyl, ethyl, propyl,butyl, pentyl and the like, including isomers thereof, more preferablyR′ is a methyl group or a primary, secondary or tertiary hydrocarbon,including isopropyl, t-butyl and the like, most preferably R′ is anisopropyl group. Optionally, an R′ group may be joined to A. It ispreferred that at least one R′ is ortho to X;

[0033] A is a bridging group joined to at least one of, preferably bothof, X and J. Bridging group A contains one or more Group 13 to 16elements from Periodic Table of Elements. More preferably A contains oneor more Group 14 elements, most preferably A is a substituted carbongroup, a di-substituted carbon group or vinyl group; and

[0034] In formula (IV) m and p are independently an integer from 0 to 5,preferably m is 2; s is an integer from 1 to 3; and q is 1 or 2, n isthe oxidation state of M minus q minus s if Q is a monovalent anion, nis (the oxidation state of M−q−s)/2, if Q is a bivalent anion or n is(the oxidation state of M−q−s)/3 if Q is a trivalent anion, and where qis 2, the two ((R′_(m)Z)XA(YJR″_(m))) of formula (IV) are bridged toeach other via a bridging group, preferably a bridging group containinga Group 14 element.

[0035] In one embodiment J is pyridine in any of the above formulae.

[0036] The transition metal compounds may be made by any method known inthe art.

[0037] In the practice if this invention, two catalysts are selected toproduce the desired product. The two or more catalysts are selected fromany of the above formulae. For example two different catalyst formformula I may be selected, or a compound from formula I or II and acompound from formula III or IV can be combined, likewise two differentcatalysts falling with the definition of formula IV may also becombined. In a preferred embodiment a compound from formula I or II isused together with at lease one compound from formulae III or IV. It ispossible to obtain a bimodal product by selecting catalysts that areknow to produce differing molecular weights.

[0038] In a preferred embodiment a first catalyst as represented byformula I or II where at least one Q group is not an oxy-adduct ischosen and the second catalyst is the same as the first catalyst systemexcept that one, two or all three of the Q groups is an oxy-adduct ofthe same Q group as is present in the first catalyst. For example if[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]ZirconiumTribenzyl is selected as the first catalyst, them[[1-(2-Pyridyl)N-1-Methylethyl]-[1-N-2,6-DiisopropylphenylAmido]][2-Methyl-1-Phenyl-2-Propoxy] Zirconium Dibenzyl may be a secondcatalyst.

[0039] For purposes of this invention and the claims thereto oxy-adductis defined to be O—R where O is oxygen and R is a C₁ to C₅₀ group whichoptionally may contain one or more heteroatoms. Preferred R groupsinclude t-butyl, t-amyl, t-hexyl, isopropyl,2-[2-methyl-1-phenyl-propyl], 2-[2-benzyl-butyl], 3-[3-benzyl-pentyl].Other possible R groups include, benzyl, methyl benzyl, ethyl benzyl andthe like. In another embodiment the oxy adduct may be represented by theformula O—B—R, where O is oxygen, B is boron and R is a C₁ to C₅₀ groupwhich optionally may contain one or more heteroatoms. Preferred R groupsinclude t-butyl, t-amyl, t-hexyl, isopropyl,2-[2-methyl-1-phenyl-propyl], 2-[2-benzyl-butyl], 3-[3-benzyl-pentyl].Other possible R groups include, benzyl, methyl benzyl, ethyl benzyl andthe like.

[0040] In a preferred embodiment the two catalysts,[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl and [[l-(2-Pyridyl)N-1-Methylethyl]-[

[0041] 1-N-2,6-Diisopropylphenyl Amido]][2-Methyl-1-Phenyl-2-Propoxy]Zirconium Dibenzyl, are used in combination with an alumoxane,preferably a methyl alumoxane, more preferably a modified methylalumoxane in a gas phase or slurry reactor to produce polyethylene,preferably high density polyethylene or alternately low densitypolyethylene. In another preferred embodiment a non-coordinating anion,such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron or atrisperfluorophenyl boron, is used in combination with the twocatalysts, [1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-DiisopropylphenylAmido] Zirconium Tribenzyl and[[1-(2-Pyridyl)N-1-Methylethyl]-[1-N-2,6-DiisopropylphenylAmido]][2-Methyl-1-Phenyl-2-Propoxy] Zirconium Dibenzyl, in a gas phaseor slurry phase reactor to produce polyolefin, preferably polyethylene.

[0042] In a preferred embodiment, the two catalyst compounds aretypically combined in a ratio of from 0.001:1 to about 10,000:1,preferably 0.5:1 to 1,000:1. In a preferred embodiment the firstcatalyst is present at from about 0.5 to about 99.5 weight % and thesecond catalyst is preset at about 99.5 to about 0.5 weight %, basedupon the weight of the two catalysts but not activators or supports,preferably 5 to 95 weight % first catalyst and 95 to 5 weight % for thesecond catalyst, preferably 10 to 90 weight % first catalyst and 90 to10 weight % for the second catalyst.

[0043] In a preferred embodiment the first catalyst is present at fromabout 0.5 to about 99.5 weight % and the second and third catalysts arepreset at about 99.5 to about 0.5 weight %, based upon the weight of thethree catalysts but not activators or supports, preferably 5 to 95weight % first catalyst, preferably 10 to 90 weight % first catalyst.

[0044] In a preferred embodiment the component that produces the lowermolecular weight is present at 10 ppm to 70 weight % based upon theweight of all the catalysts but not the activators or supports,preferably 100 ppm to 8 weight %, even more preferably 1000 ppm to 5weight %. In another embodiment the compound that produces the lowermolecular weight is present at 30 to 70 weight % based upon the weightof all the catalysts but not the activators or supports, preferably 40to 60 weight %, even more preferably 45 to 55 weight %.

[0045] In another embodiment, the component that makes the low molecularweight portion is present is an amount that will produce 20-70 weight %of the final polymer product.

[0046] The two catalysts may be activated at the same or differenttimes, before or after entry into the reactor, and before or after beingplaced on a support. In one embodiment the two catalysts are activatedby the same activator before being placed in the reactor. In anotherembodiment, one catalyst is activated before being placed in thereactor, and the second catalyst is added, optionally with no activator,the same activator or a different activator. In another embodiment thecatalysts are supported on the same support then activated with the sameactivator prior to being placed in the reactor. In another embodimentthe two catalysts are activated with the same or different activatorsthen placed upon a support before being placed in the reactor.

[0047] Likewise one or more of the catalyst systems or components may besupported on an organic or inorganic support. Typically the support canbe of any of the solid, porous supports. Typical support materialsinclude talc; inorganic oxides such as silica, magnesium chloride,alumina, silica-alumina; polymeric supports such as polyethylene,polypropylene, polystyrene; and the like. Preferred supports includesilica, clay, talc magnesium chloride and the like. Preferably thesupport is used in finely divided form. Prior to use the support ispreferably partially or completely dehydrated. The dehydration may bedone physically by calcining or by chemically converting all or part ofthe active hydroxyls. For more information on how to support catalystsplease see U.S. Pat. No. 4,808,561 which teaches how to support ametallocene catalyst system. The techniques used therein are generallyapplicable for this invention.

[0048] The catalysts may be placed on separate supports or may be placedon the same support. Likewise the activator may be placed on the samesupport as the catalyst or may be placed on a separate support. Thecatalysts/catalyst systems and/or their components need not be feed intothe reactor in the same manner. For example, one catalyst or itscomponents may slurried into the reactor on a support while the othercatalyst or components are provided in a solution.

[0049] In a preferred embodiment the catalyst system is fed into thereactor in a solution or slurry. Hydrocarbons are useful for thesolutions or slurries. For example the solution can be toluene, hexane,isopentane or a combination thereof such as toluene and isopentane ortoluene and pentane. A typical solution would be 0.02 to 0.05 molecatalyst in the hydrocarbon carrier, preferably isopentane or hexane.

[0050] In another embodiment the carrier for the catalyst system or itscomponents is a super critical fluid, such as ethane or propane. Formore information on supercritical fluids as catalyst feed agents see EP0 764 665 A2.

[0051] In another preferred embodiment the one or all of the catalystsare combined with up to 6 weight % of a metal stearate, preferably aaluminum stearate, more preferably aluminum distearate) based upon theweight of the catalyst, any support and the stearate, preferably 2 to 3weight %. In an alternate embodiment a solution of the metal stearate isfed into the reactor. These agents may be dry tumbled with the catalystor may be fed into the reactor in a solution with or without thecatalyst system or its components.

[0052] In a preferred embodiment the catalysts combined with theactivators are tumbled with 1 weight % of aluminum distearate and/or 2weight % of an antistat, such as a methoxylated amine, such as Witco'sKemamine AS-990 from ICI Specialties in Bloomington, Del. The metalstearate and/or the anti-static agent may be slurried into the reactorin mineral oil, ground into a powder then suspended in mineral oil thenfed into the reactor, or blown directly into the reactor as a powder.

[0053] More information on using aluminum stearate type additives may befound in U.S. Ser. No. 09/113,216 filed Jul. 10, 1998, which isincorporated by reference herein.

[0054] In another embodiment the two catalysts are fed into the reactorseparately.

[0055] In a preferred embodiment of the invention, (i.e. the combinationof (A). [1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl and (B).[[1-(2-Pyridyl)N-1-Methylethyl]-[1-N-2,6-DiisopropylphenylAmido]][2-Methyl-1-Phenyl-2-Propoxy] Zirconium Dibenzyl with modifiedmethyl alumoxane, it has been noted that temperature appears to affectthe balance between the active species. It seems that highertemperatures drive the conversion of one catalyst species to the other.This indicates there are opportunities for controlling the polymerproduced by varying the temperature to vary the catalyst speciespresent.

[0056] Polymerization Process of the Invention

[0057] The catalysts and catalyst systems described above are suitablefor use in a solution, gas or slurry polymerization process or acombination thereof, most preferably a gas or slurry phasepolymerization process.

[0058] In one embodiment, this invention is directed toward thesolution, slurry or gas phase polymerization reactions involving thepolymerization of one or more of monomers having from 2 to 30 carbonatoms, preferably 2-12 carbon atoms, and more preferably 2 to 8 carbonatoms. Preferred monomers include one or more of ethylene, propylene,butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, decene-1,3-methyl-pentene-1, and cyclic olefins or a combination thereof. Othermonomers can include vinyl monomers, diolefins such as dienes, polyenes,norbornene, norbomadiene, vinyl norbornene, ethylidene norbornenemonomers. Preferably a homopolymer of ethylene is produced. In anotherembodiment, a copolymer of ethylene and one or more of the monomerslisted above is produced.

[0059] In another embodiment ethylene or propylene is polymerized withat least two different comonomers to form a terpolymer. The preferredcomonomers are a combination of alpha-olefin monomers having 4 to 10carbon atoms, more preferably 4 to 8 carbon atoms, optionally with atleast one diene monomer. The preferred terpolymers include thecombinations such as ethylene/butene-1/hexene-1,ethylene/propylene/butene-1, propylene/ethylene/hexene-1,ethylene/propylene/norbornene and the like.

[0060] In a particularly preferred embodiment the process of theinvention relates to the polymerization of ethylene and at least onecomonomer having from 4 to 8 carbon atoms, preferably 4 to 7 carbonatoms. Particularly, the comonomers arebutene-1,4-methyl-pentene-1,3-methyl-pentene-1, hexene-1 and octene-1,the most preferred being hexene- 1, butene-1 and octene- 1.

[0061] Typically in a gas phase polymerization process a continuouscycle is employed where in one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228 all of which are fully incorporated herein byreference.)

[0062] The reactor pressure in a gas phase process may vary from about10 psig (69 kPa) to about 500 psig (3448 kPa), preferably from about 100psig (690 kPa) to about 500 psig (3448 kPa), preferably in the range offrom about 200 psig (1379 kPa) to about 400 psig (2759 kPa), morepreferably in the range of from about 250 psig (1724 kPa) to about 350psig (2414 kPa).

[0063] The reactor temperature in the gas phase process may vary fromabout 30° C to about 120° C., preferably from about 60° C. to about 115°C., more preferably in the range of from about 70° C. to 110° C., andmost preferably in the range of from about 70° C. to about 95° C. Inanother embodiment when high density polyethylene is desired then thereactor temperature is typically between 70 and 105° C.

[0064] The productivity of the catalyst or catalyst system in a gasphase system is influenced by the main monomer partial pressure. Thepreferred mole percent of the main monomer, ethylene or propylene,preferably ethylene, is from about 25 to 90 mole percent and thecomonomer partial pressure is in the range of from about 20 psia (138kPa) to about 300 psia (517 kPa), preferably about 75 psia (517 kPa) toabout 300 psia (2069 kPa), which are typical conditions in a gas phasepolymerization process. Also in some systems the presence of comonomercan provide a increase in productivity.

[0065] In a preferred embodiment, the reactor utilized in the presentinvention is capable and the process of the invention is producinggreater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr),still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), stilleven more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) andpreferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than100,000 lbs/hr (45,500 Kg/hr), and most preferably over 100,000 lbs/hr (45,500 Kg/hr).

[0066] Other gas phase processes contemplated by the process of theinvention include those described in U.S. Pat. Nos. 5,627,242, 5,665,818and 5,677,375, and European publications EP-A- 0 794 200, EP-A- 0 802202 and EP-B- 634 421 all of which are herein fully incorporated byreference.

[0067] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres (15 psi to 735 psi, 103kPa to 5068 kPa) and even greater and temperatures in the range of 0° C.to about 120° C. In a slurry polymerization, a suspension of solid,particulate polymer is formed in a liquid polymerization diluent mediumto which ethylene and comonomers along with catalyst are added. Thesuspension including diluent is intermittently or continuously removedfrom the reactor where the volatile components are separated from thepolymer and recycled, optionally after a distillation, to the reactor.The liquid diluent employed in the polymerization medium is typically analkane having from 3 to 7 carbon atoms, preferably a branched alkane.The medium employed should be liquid under the conditions ofpolymerization and relatively inert. When a propane medium is used theprocess must be operated above the reaction diluent critical temperatureand pressure. Preferably, a hexane or an isobutane medium is employed.

[0068] In one embodiment, a preferred polymerization technique of theinvention is referred to as a particle form polymerization, or a slurryprocess where the temperature is kept below the temperature at which thepolymer goes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 185° F. (85° C.) toabout 230° F. (110° C.). Two preferred polymerization methods for theslurry process are those employing a loop reactor and those utilizing aplurality of stirred reactors in series, parallel, or combinationsthereof. Non-limiting examples of slurry processes include continuousloop or stirred tank processes. Also, other examples of slurry processesare described in U.S. Pat. No. 4,613,484, which is herein fullyincorporated by reference.

[0069] In another embodiment, the slurry process is carried outcontinuously in a loop reactor. The catalyst as a slurry in isobutane oras a dry free flowing powder is injected regularly to the reactor loop,which is itself filled with circulating slurry of growing polymerparticles in a diluent of isobutane containing monomer and comonomer.Hydrogen, optionally, may be added as a molecular weight control. Thereactor is maintained at a pressure of about 525 psig to 625 psig (3620kPa to 4309 kPa) and at a temperature in the range of about 140° F. toabout 220° F. (about 60° C. to about 104° C.) depending on the desiredpolymer density. Reaction heat is removed through the loop wall sincemuch of the reactor is in the form of a double-jacketed pipe. The slurryis allowed to exit the reactor at regular intervals or continuously to aheated low pressure flash vessel, rotary dryer and a nitrogen purgecolumn in sequence for removal of the isobutane diluent and allunreacted monomer and comonomers. The resulting hydrocarbon free powderis then compounded for use in various applications.

[0070] In another embodiment, the reactor used in the slurry process ofthe invention is capable of and the process of the invention isproducing greater than 2000 lbs of polymer per hour (907 Kg/hr), morepreferably greater than 5000 lbs/hr (2268 Kg/hr), and most preferablygreater than 10,000 lbs/hr (4540 Kg/hr). In another embodiment theslurry reactor used in the process of the invention is producing greaterthan 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greaterthan 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500Kg/hr).

[0071] In another embodiment in the slurry process of the invention thetotal reactor pressure is in the range of from 400 psig (2758 kPa) to800 psig (5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig(4827 kPa), more preferably 500 psig (3448 kPa) to about 650 psig (4482kPa), most preferably from about 525 psig (3620 kPa) to 625 psig (4309kPa).

[0072] In yet another embodiment in the slurry process of the inventionthe concentration of ethylene in the reactor liquid medium is in therange of from about 1 to 10 weight percent, preferably from about 2 toabout 7 weight percent, more preferably from about 2.5 to about 6 weightpercent, most preferably from about 3 to about 6 weight percent.

[0073] Another process of the invention is where the process, preferablya slurry or gas phase process is operated in the absence of oressentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This process isdescribed in PCT publication WO 96/08520 and U.S. Pat. No. 5,712,352,which are herein fully incorporated by reference.

[0074] In another embodiment the process is run with scavengers. Typicalscavengers include trimethyl aluminum, tri-isobutyl aluminum and anexcess of alumoxane or modified alumoxane.

[0075] The proportions of the components of the feed catalyst solutioncan be varied to alter molecular weight and other properties. Forexample altering the catalyst ratios will alter flow index, melt index,melt flow ratio and/or density. For example, in a system where acatalyst represented by formula I and a catalyst represented by formulaIV are combined, if the proportion of a catalyst represented by formulaIV is increased then, more lower molecular weight material is producedthus increasing flow index, altering the molecular weight distribution.In a preferred embodiment the catalyst that produces the lower molecularweight component is present at a value to produce 45-65 weight % of thefinal polymer product. For some applications such as films thecombination of 55-35 weight % of (A).[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl and 45-65 weight % of (B).[[1-(2-Pyridyl)N-1-Methylethyl]-[1-N-2,6-DiisopropylphenylAmido]][2-Methyl-1-Phenyl-2-Propoxy] Zirconium Dibenzyl has been foundeffective.

[0076] Another method to alter the molecular weight is to add hydrogento the system by increasing the hydrogen ethylene ratio. A method tocontrol the density is altering the comonomer content.

[0077] A method to control molecular weight distribution (Mw/Mn), flowindex, and/or density comprising altering on line in a commercial scalegas phase reactor (i.e. having a volume of 1500 cubic feet or more) thereaction temp and/or the catalyst ratio in the intimately mixed catalystsolution and/or the hydrogen concentration and/or the activator totransition metal ratio, such as the aluminum/zirconium ratio is alsoprovided herein.

[0078] Injection and mixing temperatures also provide a means to alterproduct properties as temperature affects activation and/or solventevaporation and thus alters the catalyst composition and hence altersthe final product.

[0079] The sequence and timing of activation also provides anopportunity to alter the catalyst composition and thus the finalproduct. For example higher concentrations of methyl alumoxane in asystem comprising (A).[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl and (B).[[1-(2-Pyridyl)N-1-Methylethyl]-[1-N-2,6-DiisopropylphenylAmido]][2-Methyl-1-Phenyl-2-Propoxy] Zirconium Dibenzyl will alter thebalance of products formed by the two catalysts. This includes higherconcentrations during activation and/or mixing and/or transport and/orin spraying into the reactor. Likewise we have noted that increasing thehydrocarbon carrier in the catalyst feed increased the amount of lowermolecular weight fraction produced.

[0080] One can also vary the product by altering the reactiontemperature. We have noted that raising the reaction temperatureincreased the amount of the higher molecular weight component andunusually the two modes in the size exclusion chromatography graph movedcloser together (that is the Mw/Mn became lower when compared to thesame system at a lower temperature).

[0081] One can also vary the molecular weight distribution by varyingthe reactor temperature, varying the temperature of the catalyst systembefore it enters the reactor, varying the catalyst to activator ratio,varying the volume of the carrier, and/or contacting the transitionmetal component with solvent prior to activation with the activator.

[0082] In a preferred embodiment the ratio of the first catalyst to thesecond catalyst is 5:95 to 95:5, preferably 25:75 to 75:25, even morepreferably 40:60 to 60:40.

[0083] In another preferred embodiment the catalyst system in is liquidform and is introduced into the reactor into a resin particle lean zone.For information on how to introduce a liquid catalyst system into afluidized bed polymerization into a particle lean zone, please see U.S.Pat. No. 5,693,727, which is incorporated by reference herein.

[0084] In a preferred embodiment, the polyolefin recovered typically hasa melt index as measured by ASTM D-1238, Condition E, at 190° C. of 1g/10 min or less. In a preferred embodiment the polyolefin is ethylenehomopolymer or copolymer. The comonomer is preferably a C3 to C20 linearbranched or cyclic monomer, and in one embodiment is a C3 to C12 linearor branched alpha-olefin, preferably propylene, hexene, pentene, hexene,heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-1,3-methylpentene-1,3,5,5-trimethyl hexene 1, and the like.

[0085] In a preferred embodiment the catalyst system described above isused to make a high density polyethylene having a density of between0.925 and 0.965 g/cm³ (as measured by ASTM 2839), and/or a melt index of1.0 or less g/10 min or less (as measured by ASTM D-1238, Condition E,at 190° C.). In another embodiment the catalyst system described aboveis used to make a polyethylene of 0.85 to 0.924 g/cm³.

[0086] The polyolefins then can be made into films, molded articles,sheets and the like. The films may be formed by any of the conventionaltechnique known in the art including extrusion, co-extrusion,lamination, blowing and casting. The film may be obtained by the flatfilm or tubular process which may be followed by orientation in anuniaxial direction or in two mutually perpendicular directions in theplane of the film. Particularly preferred methods to form the polymersinto films include extrusion or coextrusion on a blown or cast filmline.

[0087] The films produced may further contain additives such as slip,antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers,antistats, polymer processing aids, neutralizers, lubricants,surfactants, pigments, dyes and nucleating agents. Preferred additivesinclude silicon dioxide, synthetic silica, titanium dioxide,polydimethylsiloxane, calcium carbonate, metal stearates, calciumstearate, zinc stearate, talc, BaSO₄, diatomaceous earth, wax, carbonblack, flame retarding additives, low molecular weight resins, glassbeads and the like. The additives may be present in the typicallyeffective amounts well known in the art, such as 0.001 weight % to 10weight %.

EXAMPLES

[0088] MFR Melt Flow Ratio was measured by ASTM 1238.

[0089] BBF (butyl branch frequency per 1000 carbon atoms) was measuredby infrared spectroscopy as described in U.S. Pat. No. 5,527,752.

[0090] PDI (polydispersity index) is equivalent to Mw/Mn and wasmeasured by Size Exclusion Chromotography.

[0091] Mn and Mw were measured by gel permeation chromatography on awaters 150° C. GPC instrument equipped with differential refractionindex detectors. The GPC columns were calibrated by running a series ofnarrow polystyrene standards and the molecular weights were calculatedusing Mark Houwink coefficients for the polymer is question.

[0092] Melt Index (MI) was measured by the procedure according to ASTM1238, condition E.

[0093] Melt Index Ratio (MIR) is the ratio of I₂₁ over I₂ as measured bythe procedure according to ASTM D 1238.

[0094] Density is measured according to ASTM D 1505.

Example 1

[0095] Preparation Of[1-(2-Pyridyl)N-1-Methylethyl[]1-N-2,6-Diisopropylphenyl]Amine

[0096] In a dry box, 22.45 mmol (6.34 g)2-acetylpyridine(2,6-diisopropylphenylimine) were charged to a 250 mLround bottom flask equipped with a stir bar and septa. The flask wassealed, removed from the dry box and placed under nitrogen purge. Drytoluene (50 mL) was added and stirred to dissolve the ligand. The vesselwas chilled to 0° C. in a wet ice bath. Trimethyl aluminum (Aldrich, 2.0M in toluene) was added dropwise over ten minutes. The temperature ofthe reaction was not allowed to exceed 10° C. When addition of thetrimethyl aluminum was complete, the mixture was allowed to warm slowlyto room temperature, and then was then placed in an oil bath and heatedto 40° C. for 25 minutes. The vessel was removed from the oil bath andplaced in an ice bath. A dropping funnel containing 100 mL of 5% KOH wasattached to the flask. The caustic was charged to the reaction dropwiseover a 1 hour span. The mixture was transferred to a separatory funnel.The aqueous layer was removed. The solvent layer was washed with 100 mLwater then 100 mL brine. The red-brown liquid product was dried overNa₂SO₄, vacuum stripped and placed under high vacuum over night.

[0097] 80 mL of red-brown liquid was transferred to a 200 mL Schlenkflask equipped with a stir bar. A distillation head with a dry icecondenser was attached to the flask. The mixture was vacuum distilledyielding approximately 70 g of dark yellow viscous liquid product.

Example 2

[0098] Preparation Of[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl

[0099] In a darkened room and darkened dry box, 5.0 mmol (1.45 g) of theligand made in Example 1 were charged to a 100 mL Schlenk tube equippedwith a stir bar. The ligand was dissolved in 5 mL of toluene. To asecond vessel equipped with a stir bar was charged 5.5 mmol (2.5g)tetrabenzyl zirconium and 10 mL toluene.

[0100] The ligand solution was transferred into the tetrabenzylzirconium solution. The vessel was covered with foil and allowed to stirat room temperature in the dry box. After 6 hours at room temperature 80mL dry hexane was added to the reaction solution and allowed to stirovernight. The reaction mixture was filtered through a medium porosityfrit with approximately 2 g pale yellow solids collected.

Example 3

[0101] Preparation Of[[1-(2-Pyridyl)N-1-Methylethyl]-[1-N-2,6-DiisopropylphenylAmido]][2-Methyl-1-Phenyl-2-Propoxy] Zirconium Dibenzyl

[0102] To an oven-dried, cooled, purged and sealed GC vial was charged0.10 mL dried acetone. The GC vial was sealed in a shell vial and takeninto the dry box. In a darkened room and darkened dry box 2.0 mmol (1.3g) of the material made in Example 2 and 9 mL toluene were charged to 1100 mL Schlenk flask equipped with a stir bar. To a second GC vial wascharged 2.0 mmol (146 μL) acetone and 1.0 mL toluene. Theacetone/toluene solution was transferred dropwise via syringe into thestirred solution of [1-(2pyridyl)N-1-methylethyl][1-N-2,6-diisopropylphenylamido] zirconoum tribenzyl.The vessel was covered with foil and allowed to stir at room temperaturein the dry box overnight.

[0103] The reaction solution was vacuum stripped to a tacky orangeresidue. Dry hexane (20 mL) was added and the residue stirredvigorously, then vacuum stripped again to a yellow-orange glass. Hexanewas added again and vigorously stirred. The vessel was placed in afreezer (−24° C.) for approximately 2 hours. The mixture was filteredthrough a medium porosity frit. Pale yellow solids (0.8 g) werecollected. Slow deliberate feeding of the acetone with good mixingappears best.

Example 4

[0104] A series of bimodal ethylene/hexene copolymers were made in alaboratory scale, slurry phase reactor using mixed catalyst compositionsof the complexes prepared in Example 2 and Example 3 according to theinvention with modified methyl alumoxane (MMAO) cocatalyst type 3A(commercially available from Akzo Chemicals, Inc. under the trade nameModified Methylalumoxane type 3A, covered under U.S. Pat. No.5,041,584).

[0105] In each case, the catalyst composition was prepared by preparingmixtures of the complexes from Example 2 and Example 3 in toluene, andthen contacting with MMAO solution (7.0 wt % Al in heptane) in thepresence of 0.1 mL 1-hexene. Polymerization reaction conditions were 85°C., 85 psi (586 kPa) ethylene, 43 mL of 1-hexene, 0.5 micromole Zr, anda MMAO/Zr mole ratio of 1,000:1. Complex ratios are expressed as themole ratios of the complex prepared in Example 3 to the complex preparedin Example 2. Results are shown in Table 1 below. TABLE 1 ActivityComplex gPE/mmolcat/ I2 BBF Ratio 100 psi C2/hr dg/min MFR per 1000 C'sPDI 100:0  139765 162.2 1.82 6.28 11.18 90:10 291765 13.49 61.66 10.0825.84 80:20 175529 0.05 1,027 7.54 23.74 60:40 235765 0.0085 317.4 9.9228.24 50:50 189647 0.012 173.1 11.01 30.25

[0106] Size Exclusion Chromatography was conducted on the resinsprepared in Table 1. The results clearly demonstrate an increase in thehigh molecular weight component with increasing concentrations of thecomplex from Example 2. The relative amounts of the complexes fromExample 3 and Example 2 respectively reflect the low and high molecularweight components in these bimodal resins. This shows that the twocatalysts are highly compatible.

Example 5

[0107] An ethylene hexene copolymer was produced in a 14 inch pilotplant gas phase reactor operating at 85° C., 220 psi ( 1517 kPa) havinga water cooled heat exchanger. The ethylene was fed in at a rate ofabout 55 pounds of ethylene per hour (25 kg/hr) and hexene was fed in at1.4 pounds per hour(0.64 kg/hr) and hydrogen was fed in at rate of 0.021pounds per hour (0.01 kg/hr) to make about 35 pounds per hour (15.9kg/hr) of polymer. Total reactor pressure was 350 psi (2413 kPa). Thenitrogen was present at about 3-7 pounds/hour (1.4 kg-3.2 kg). Thereactor was equipped with a plenum set at 1800 pounds per hour (818.2kg/hr) with a single hole tapered nozzel injector having a 0.055 inch(0.14 cm) inside diameter. (The plenum is a device used to create aparticle lean zone in a fluidized bed gas phase reactor. For moreinformation on plenum usage see U.S. Pat. No. 5,693,727) This procedurewas repeated and one or more of the reaction temperature, the Al/Zrratio, the reaction temperature, the injection temperature or thehydrocarbon feed carrier were varied as reported in Table 2. TABLE 2Example Rxn temp Wt % low Mw Catalyst Mw/Mn Al:Zr ratio A 85 60 3 14350:1::Al:Zr B 90 57 3 16 360:1::Al:Zr C 95 51 3 12 350:1::Al:Zr D 105 35 3 11 350:1::Al:Zr E 85 22 60/40 450:1::Al:Zr 2:3 F 85 70 3 72:1::Al:Zr

Example 6

[0108] The example above was repeated with the catalysts produced inexamples 2 and 3 except that the polymerization conditions were 85° C.,220 psi ( 1517 kPa)C₂, 500:1 Al/Zr, catalyst feed 10 cc/hr, MMAO feed300 cc/hr (2.3 wt % Al in hexane). The ratio of the two catalysts wasvaried. TABLE 3 Catalyst ratio Activity I2 density 2/3 (g PE/mmolZr/hr)dg/min MFR g/cm³ 60/40 15,651 0.196 51.47 0.9455 40/60 17,929 0.15059.89 0.9475 20/80 16,905 0.165 63.45 0.9498  0/100 16,061 0.167 76.270.951  80/20 40,048 0.150 52.08 0.9422

Example 7

[0109] Two ethylene hexene copolymers were produced in an 8 foot (2.4 m)diameter gas phase reactor (having a volume of about 2000 cubic feet)having a bed height of 38 feet(11.6 m). The ethylene feed rate was about8000 to 9000 pounds per hour (3636-4090 kg/hr). The hexene feed rate wasabout 200-230 pounds per hour (90.0-104.5 kg/hr). The hydrogen feed ratewas about 1-2 pounds per hour (2.2 to 4.4 kg/hr). The copolymer wasproduced at 8000-9000 pounds per hour(3636-4090 kg/hr). 30-60 pounds perhour of nitrogen (13.6-27.3 kg/hr) were fed into the reactor. Thereactor was equipped with a plenum set at 50,000 pounds per hour (22,727kg/hr) and three hole nozzel having a diameter of 0.125 inches (0.32 cm)tapering to a diameter of 0.05 inches (0.13 cm) at the central hole andtwo other holes 0.30 inches ( 0.76 cm)from the nozzel end perpendicularto the flow of the gas and {fraction (5/64)}ths of an inch (0.20cm)wide. The cycle gas velocity was about 2-2.2 feet per sec (60-67cm/sec). The injection temperature was 22° C. for the first run and 80°C. for the second run. The catalyst was the catalyst produced in example3 combined with 2 weight % modified methyl alumoxane 3A in an Al:Zrratio of 150: 1. The first run produced an ethylene hexene copolymerhaving 44 weight % lower molecular weight portion and the second runproduced 36 weight % of lower molecular weight portion.

Example 8

[0110] Five 0.02 Molar solutions in toluene of the compounds prepared inexamples 2 and 3 were prepared in ratios of 80/20, 60/40, 40/60, 20/80and 0/100. They were polymerized according to the procedure in example 5using modified methyl alumoxane 3A as the cocatalyst. The bedtemperature was maintained at 85° C. The ethylene partial pressure was220 psi (1537 kPa) and the Al:Zr ratio was 500:1. 80/20 60/40 0/60 20/800/100 C6/C2 Ratio 8.1 -9.1 6.6-7.7 6.1-6.7 5.4-5.6 5.4-5.7 (× 10⁻³)H2/C2 Ratio 23.7-25.5 17.5-18.6 14.0 12.3-12.6 12.1-12.2 (× 10⁻³)Production 28 6 26 26 27 Rate (pph) Activity 19000 17500 15000 1610017500 GPE/mmolZr/h Melt Index 0.15-0.26 0.17-0.26 0.13-0.34 0.12-0.170.16-0.21 dg/min Flow Index 8.07-12.3  0.95-12.88  8.81-14.07 9.68-10.95 12.53-14.50 dg/min Melt Flow Rati 39.87-55.63 46.37-64.3932.96-65.75 61.24-81.87 70.73-77.83 MFR Density g/cc 0.942-0.944.0945-0.947 0.947-0.950 0.950-0.951 0.9951-0.952 

Example 9

[0111] SYNTHESIS OF[1-(2-PYRIDYL)-N-1-METHYLETHYL][1-N-2,6DIISOPROPYLPHENYLAMIDO][3-BENZYL-3-PENTOXY]ZIRCONIUM DIBENZYL

[0112] Diethyl ketone (40 mmol, 4.0 mL, Aldrich, 3-Pentanone, 99.5%,[86.13]) was dissolved in 96 mL of dry toluene. The diethyl ketonesolution was slowly transferred into a stirring solution (400 mL, 0.125Min toluene) of the complex prepared in Example 2. The resulting solutionwas allowed to stir over night.

Example 10

[0113] SYNTHESIS OF [1-(2-PYRIDYL)-N-1-METHYLETHYL[]1-N-2,6DIISOPROPYLPHENYLAMIDO][2-BENZYL-2-BUTOXY] ZIRCONIUM DIBENZYL

[0114] Methyl ethyl ketone (40 mmol, 3.6 mL, Aldrich, 2-Butanone,99.5%,) was dissolved in 100 mL of dry toluene. The methyl ethyl ketonesolution was slowly transferred into a stirring solution (400 mL, 0.125Min toluene). of the complex prepared in Example 2. The resultingsolution was allowed to stir over night.

Example 11

[0115] In a dry box, 1-hexene (0.1 mLs, alumina dried) was charged to anoven dried, 4 dram glass vial. The complex from Example 2 (0.25micromoles, 2.0 microliters, a 0.125M solution in toluene), and thecomplex prepared in Example 9 (0.25 μmoles, 3.7 microliters, a 0.067Msolution in deuterated benzene) was added to the 1-hexene resulting in apale yellow solution. MMAO type 3A (0.25 mmoles) was then added to thevial resulting in a pale yellow reaction solution. The reaction solutionwas charged to the reactor containing 600 mLs n-hexane, 43 mLs 1-hexene,and 0.13 mLs (0.25 mmoles) MMAO type 3A, and run at 70° C., 85 psiethylene, and 10 psi hydrogen for 30 minutes. The reaction produced 26.3g of polyethylene resin (activity=123765 g polyethylene/mmoleZr/hour/100 psi ethylene, I2=28.49, I21=838, MFR=29.4, BBF=7.63). SizeExclusion Chromatography (SEC) revealed the following molecular weightResults: Mn=12611, Mw=50585, PDI=4.01. The SEC graph is presented asFIG. 6.

Example 12

[0116] In a dry box, 1-hexene (0.1 mLs, alumina dried) was charged to anoven dried, 4 dram glass vial. The complex from Example 2 (0.25 μmoles,, a 0.125M solution in toluene), and the complex from Example 10 (0.25μmoles, , an 0.080M solution in toluene) was added to the 1-hexeneresulting in a yellow solution. MMAO type 3A (0.25 mmoles) was thenadded to the vial resulting in yellow reaction solution. The reactionsolution was charged to a 1L slurry reactor containing 600 mLs n-hexane,43 mLs 1-hexene, and 0.13 mLs (0.25 mmoles) MMAO type 3A, and run at 70°C., 85 psi ethylene, and 10 psi hydrogen for 30 minutes The reactionproduced 30.7 g of resin (activity=144471 g polyethylene/mmoleZr/hour/100 psi ethylene, I2=11.47, I21=468, MFR=40.8, BBF 7.53).: SizeExclusion Chromatography (SEC) revealed the following molecular weightResults: Mn=12794, Mw=62404, PDI=4.88. The SEC graph is presented asFIG. 7.

[0117] All documents described herein are incorporated by referenceherein, including any priority documents and/or testing procedures. Asis apparent form the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly it is not intended thatthe invention be limited thereby.

1. An olefin polymerization catalyst composition comprising the productof the combination of at least one activator and at least two differenttransition metal compounds each of which is represented by the formula:((Z)XA_(t)(YJ))_(q)MQ_(n)  (I) where M is a metal selected from Group 3to 13 or lanthanide and actinide series of the Periodic Table ofElements; Q is bonded to M and each Q is a monovalent, divalent ortrivalent anion; X and Y are bonded to M; X and Y are independently C ora heteroatom, provided that at least one of X and Y is a heteroatom andY is contained in a heterocyclic ring J, where J comprises from 2 to 50non-hydrogen atoms; Z is bonded to X, where Z comprises 1 to 50non-hydrogen atoms; t is O or 1; when t is 1, A is a bridging groupjoined to at least one of X, Y or J; q is 1 or 2; n is the oxidationstate of M minus q minus 1 if Q is a monovalent anion, n is (theoxidation state of M−q)/2, if Q is a bivalent anion or n is (theoxidation state of M−q)/3 if Q is a trivalent anion.
 2. The catalystsystem of claim 1 wherein t is 1, Z is bound to one or more R′ groupsindependently selected from group consisting of hydrogen or linear,branched, alkyl radicals or cyclic alkyl, alkenyl, alkynyl or arylradicals, two or more R′ groups may be joined to form a cyclic moiety,optionally, an R′ group may be joined to A; and J is substituted withtwo or more R″ groups independently selected from the group consistingof hydrogen or linear, branched, cyclic, alkyl radicals, or alkenyl,alkynyl, alkoxy, aryl or aryloxy radicals and two or more R″ groups maybe joined to form a cyclic moiety, optionally, an R″ may be joined to A.3. The catalyst system of claim 1 wherein at least one of the transitionmetal catalyst is represented by the formula:((Z)XA_(t)(YJ))_(q)MQ_(m)T_(s) where M is a metal selected from Group 3to 13 or lanthanide and actinide series of the Periodic Table ofElements; T is bonded to M and is an element from Group 13 to 16, and Tmay also be bound to one or more C1 to C50 groups optionally containingone or more heteroatoms, Q is bonded to M and each Q is a monovalent,divalent or trivalent anion; X and Y are bonded to M; X and Y areindependently C or a heteroatom, provided that at least one of X and Yis a heteroatom, Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, Z comprises 1 to 50non-hydrogen atoms, t is 0 or 1; when t is 1, A is a bridging groupjoined to at least one of X, Y or J, preferably X and J; q is 1 or 2; mis the oxidation state of M minus q minus s if Q is a monovalent anion,m is (the oxidation state of M−s)/2, if Q is a bivalent anion or m is(the oxidation state of M−q−s)/3 if Q is a trivalent anion, s is 1, 2 or3.
 4. The catalyst system of claim 3 wherein t is 1, Z is bound to oneor more R′ groups independently selected from group consisting ofhydrogen or linear, branched, alkyl radicals or cyclic alkyl, alkenyl,alkynyl or aryl radicals, two or more R′ groups may be joined to form acyclic moiety, optionally, an R′ group may be joined to A; and J issubstituted with two or more R″ groups independently selected from thegroup consisting of hydrogen or linear, branched, cyclic, alkylradicals, or alkenyl, alkynyl, alkoxy, aryl or aryloxy radicals and twoor more R″ groups may be joined to form a cyclic moiety, optionally, anR″ may be joined to A.
 5. The catalyst system of claim 3 wherein T is ahydrocarboxy group, a boronate group, an amide group or acyclopentadienide group.
 6. The catalyst system of claim 3 wherein T isan alkoxide, acetylacetonate, or carboxylate or a phenoxide.
 7. Thecatalyst system of claim 1 wherein n is 2 or 3 and the second catalystis the same as the first catalyst except that one Q group is ahydrocarboxy group, a boronate or an amide.
 8. The catalyst system ofclaim 1 wherein n is 2 or 3 and the second catalyst is the same as thefirst catalyst except that one Q group is an alkoxide, phenoxide,acetylacetonate, carboxylate, cyclopentadienyl, flourenyls or an indenylgroup.
 9. The catalyst system of claim 1 wherein n is 2 or 3 and thesecond catalyst is the same as the first catalyst except that one Qgroup of the second catalyst is a hydrocarboxy adduct of the analogous Qgroup on the first catalyst.
 10. The catalyst system of claim 9 whereinthe hydrocarboxy adduct is an alkoxide adduct, a boronate or an amideadduct.
 11. The catalyst system of claim 9 wherein the hydrocarboxyadduct is a phenoxide adduct, acetylacetonate adduct, or carboxylateadduct.
 12. The catalyst system of claim 1 wherein n is 2 or 3 and thesecond catalyst is the same as the first catalyst except that one Qgroup of the second catalyst is a cyclopentadienyl adduct, a flourenyladduct or an indenyl adduct of the analogous Q group on the firstcatalyst.
 13. The composition of claim 1 wherein M is titanium,zirconium or hafnium in all the transition metal compounds.
 14. Thecomposition of claim 1 wherein each Q is independently selected from thegroup consisting of boronates, halogens, hydrogen, alkyl, aryl, alkenyl,alkylaryl, arylalkyl, hydrocarboxy or phenoxy radicals having 1-20carbon atoms, amides, phosphides, sulfides, silylalkyls, diketonates,and carboxylates.
 15. The composition of claim 1 wherein X and Y areindependently nitrogen, oxygen, sulfur or phosphorus.
 16. Thecomposition of claim 1 wherein Z is an aryl group.
 17. The compositionof claim 1 wherein J is pyridine.
 18. The composition of claim 1 whereinthe two different transition metal compounds are[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl and[[1-(2-Pyridyl)N-1-Methylethyl]-[1-N-2,6-DiisopropylphenylAmido]][2-Methyl-1-Phenyl-2-Propoxy] Zirconium Dibenzyl.
 19. Thecomposition of claim 1 wherein the activator is an alumoxane.
 20. Thecomposition of claim 1 wherein the activator is a non-coordinatinganion.
 21. The composition of claim 3 wherein the activator is analumoxane.
 22. The composition of claim 3 wherein the activator is amodified methyl alumoxane.
 23. The composition of claim 1 furthercomprising a metal stearate.
 24. The composition of claim 1 furthercomprising aluminum distearate.
 25. The composition of claim 1 wherein Xand Y are nitrogen.
 26. A process to polymerize olefins comprisingcontacting an olefin with a catalyst composition comprising andactivator and at least two different transition metal compounds each ofwhich is represented by the formula: ((Z)XA_(t)(YJ))_(q)MQ_(n)  (I)where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, divalent or trivalent anion; X and Y are bondedto M; X and Y are independently C or a heteroatom, provided that atleast one of X and Y is a heteroatom and Y is contained in aheterocyclic ring J, where J comprises from 2 to 50 non-hydrogen atoms;Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms; t is 0or 1; when t is 1, A is a bridging group joined to at least one of X, Yor J; q is 1 or 2; n is the oxidation state of M minus q if Q is amonovalent anion, n is (the oxidation state of M−q)/2, if Q is abivalent anion or n is (the oxidation state of M−q)/3 if Q is atrivalent anion.
 27. The process of claim 26 wherein t is 1, Z is boundto one or more R′ groups independently selected from group consisting ofhydrogen or linear, branched, alkyl radicals or cyclic alkyl, alkenyl,alkynyl or aryl radicals, two or more R′ groups may be joined to form acyclic moiety, optionally, an R′ group may be joined to A; and J issubstituted with two or more R″ groups independently selected from thegroup consisting of hydrogen or linear, branched, cyclic, alkylradicals, or alkenyl, alkynyl, alkoxy, aryl or aryloxy radicals and twoor more R″ groups may be joined to form a cyclic moiety, optionally, anR″ may be joined to A.
 28. The process of claim 26 wherein at least oneof the transition metal catalyst is represented by the formula:((Z)XA_(t)(YJ))_(q)MQ_(m)T_(s) where M is a metal selected from Group 3to 13 or lanthanide and actinide series of the Periodic Table ofElements; T is bonded to M and is an element from Group 13 to 16, and Tmay also be bound to one or more C1 to C50 groups optionally containingone or more heteroatoms, Q is bonded to M and each Q is a monovalent,divalent or trivalent anion; X and Y are bonded to M; X and Y areindependently C or a heteroatom, provided that at least one of X and Yis a heteroatom, Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, Z comprises 1 to 50non-hydrogen atoms, t is 0 or 1; when t is 1, A is a bridging groupjoined to at least one of X, Y or J, preferably X and J; q is 1 or 2; mis the oxidation state of M minus q minus s if Q is a monovalent anion,m is (the oxidation state of M−q−s)/2, if Q is a bivalent anion or m is(the oxidation state of M−q−s)/3 if Q is a trivalent anion, s is 1, 2 or3.
 29. The process of claim 28 wherein t is 1, Z is bound to one or moreR′ groups independently selected from group consisting of hydrogen orlinear, branched, alkyl radicals or cyclic alkyl, alkenyl, alkynyl oraryl radicals, two or more R′ groups may be joined to form a cyclicmoiety, optionally, an R′ group may be joined to A; and J is substitutedwith two or more R″ groups independently selected from the groupconsisting of hydrogen or linear, branched, cyclic, alkyl radicals, oralkenyl, alkynyl, alkoxy, aryl or aryloxy radicals and two or more R″groups may be joined to form a cyclic moiety, optionally, an R″ may bejoined to A.
 30. The process of claim 28 wherein T is a hydrocarboxygroup, a boronate or an amide, preferably an alkoxide, phenoxide,acetylacetonate, or carboxylate or a cyclopentadienide group.
 31. Theprocess of claim 28 wherein T is an alkoxide or a phenoxide.
 32. Theprocess of claim 26 wherein n is 2 or 3 and the second catalyst is thesame as the first catalyst except that one Q group is a hydrocarboxygroup, a boronate or an amide.
 33. The process of claim 26 wherein n is2 or 3 and the second catalyst is the same as the first catalyst exceptthat one Q group is an alkoxide, phenoxide, acetylacetonate,carboxylate, cyclopentadienyl, flourenyls or an indenyl group.
 34. Theprocess of claim 26 wherein n is 2 or 3 and the second catalyst is thesame as the first catalyst except that one Q group of the secondcatalyst is a hydrocarboxy adduct of the analogous Q group on the firstcatalyst.
 35. The process of claim 34 wherein the hydrocarboxy adduct isan alkoxide adduct, a boronate or an amide adduct.
 36. The process ofclaim 34 wherein the hydrocarboxy adduct is a phenoxide adduct,acetylacetonate adduct, or carboxylate adduct.
 37. The process of claim26 wherein n is 2 or 3 and the second catalyst is the same as the firstcatalyst except that one Q group of the second catalyst is acyclopentadienyl adduct, a flourenyls adduct or an indenyl adduct of theanalogous Q group on the first catalyst.
 38. The process of claim 26wherein M is titanium, zirconium or hafnium.
 39. The process of claim 26wherein M is zirconium.
 40. The process of claim 26 wherein each Q isindependently selected from the group consisting of boronates, halogens,hydrogen, alkyl, aryl, alkenyl, alkylaryl, arylalkyl, hydrocarboxy orphenoxy radicals having 1-20 carbon atoms, amides, phosphides, sulfides,silylalkyls, diketonates, and carboxylates.
 41. The process of claim 26wherein X and Y are independently nitrogen, oxygen, sulfur orphosphorus.
 42. The process of claim 26 wherein Z is an aryl group. 43.The process of claim 26 wherein J is pyridine.
 44. The process of claim26 wherein the two different transition metal compounds are[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl and[[1-(2-Pyridyl)N-1-Methylethyl]-[l-N-2,6-DiisopropylphenylAmido]][2-Methyl-1-Phenyl-2-Propoxy] Zirconium Dibenzyl.
 45. The processof claim 26 wherein the activator is an alumoxane.
 46. The process ofclaim 26 wherein the activator is a non-coordinating anion.
 48. Theprocess of claim 26 wherein the activator is a modified methylalumoxane.
 49. The process of claim 26 wherein the olefin is a monomerhaving 2 to 30 carbon atoms.
 50. The process of claim 26 wherein theolefin comprises ethylene.
 51. The process of claim 26 wherein theolefin comprises ethylene and one or more of propylene, butene-1,pentene-1,4-methyl-pentene-1, hexene-1, octene-1, decene-1, and3-methyl-pentene-1.
 52. The process of claim 26 wherein the reactortemperature is varied to cause a change in the Mw/Mn of the polymerproduced as compared to the polymer produced before the temperature isvaried.
 53. The process of claim 26 wherein the temperature of thecatalyst system before the catalyst system is introduced into thereactor is varied to cause a change in the Mw/Mn of the polymer producedas compared to the polymer produced before the temperature is varied.54. The process of claim 26 wherein the activator to catalyst ratio isvaried to cause a change in the Mw/Mn of the polymer produced ascompared to the polymer produced before the ratio change.
 55. Theprocess of claim 26 wherein the ratio of the first catalyst to thesecond catalyst is 5:95 to 95:5.
 55. The process of claim 26 wherein theratio of the first catalyst to the second catalyst is 25:75 to 75:25.56. The process of claim 26 wherein the ratio of the first catalyst tothe second catalyst is 40:60 to 60:40.
 57. The process of claim 26wherein the transition metal compounds are contacted with solvent priorto contact with the activator.
 58. The process of claim 26 furthercomprising a method to control molecular weight distribution (Mw/Mn),flow index, and/or density comprising altering on line in a gas phasereactor having a volume of 1500 cubic feet or more the reaction tempand/or the catalyst ratio in the intimately mixed catalyst solutionand/or the hydrogen concentration and/or the activator to transitionmetal ratio.